紫精修饰多功能Eu(Ⅲ)配合物的荧光开关、非线性光学和光电活性

doi:10.11944/j.issn.1000-0518.2017.09.170160

摘要/Abstract

摘要：

利用紫精功能化的配体1-(3,5-二羧基苄基)-4,4'-联吡啶硝酸盐 (H₂L⁺NO^-₃)与Eu(Ⅲ)离子在溶剂热条件下得到一个金属有机配合物{[Eu(μ₂-OH)(L)(HCO₂)]·H₂O}_n(1),其中甲酸阴离子来自于溶剂DMF(N,N'-二甲基甲酰胺)分子的原位分解。单晶X射线衍射表明配合物1是一个手性的二维层状结构。配合物1呈现出可逆的、快速响应的光致变色特性。在光热作用下,它表现为肉眼可见的从浅黄到深绿色的可逆颜色改变,这种着色/脱色过程可以循环多次,具有很好的可逆性。结构分析表明,供体羧酸基团和受体紫精单元之间以及配合物中π••••π相互作用为电子转移提供了有效的路径,从而导致光致变色行为的发生。该手性配合物不仅呈现出光调节荧光特性,还具有二阶非线性光学(SHG)开关性质。在相同粒径的测试条件下,配合物1的SHG信号强度大约是磷酸二氢钾(KDP)的3.8倍。此外,配合物1的表面光电压测定显示它呈现出光电活性。

关键词: 紫精, Eu(Ⅲ)配合物, 荧光开关, 非线性光学特性, 光电活性

Abstract:

The solvothermal reaction of a viologen-functionalized aromatic dicarboxylate ligand 1-(3,5-dicarboxybenzyl)-4,4'-bipyridinium nitrate(H₂L⁺NO^-₃) with Eu(Ⅲ) leads to the formation of a new metal-organic complex {[Eu(μ₂-OH)(L)(HCO₂)]·H₂O}_n(1), in which the formate anions come from the in situ decomposition of solvent dimethylformamide(DMF). Single-crystal X-ray analysis revealed that complex 1 has chirality and diaplays a two-dimensional layer structure. Complex 1 manifests fast photoresponsive and reversibile photochromic properties. It gives an eye-detectable color change from pale-yellow to dark green upon exposure to light, and the coloring/fading processes can repeat several cycles. The structural analysis demonstrated that the electrons transfer from carboxylate donors to viologen acceptor as well as the π••••π interaction offers reasonable electron-transfer pathways for the photochromic process. Interestingly, the synthesized solid-state chiral crystalline material not only exhibits tunable luminescence in response to light, but also shows photoswitching nonlinear optical(NLO) activity, and the second-harmonic generation(SHG) efficiency is approximately 3.8 times that of potassium dihydrogen phosphate(KDP) in the same particle size. Moreover, surface photovoltage spectroscopy(SPS) of complex 1 has been investigated and the result indicates it exhibits interesting photovoltaic activity.

Key words: multi-functional, viologen-based, Eu(Ⅲ) complex, photoswitchable luminescence, nonlinear optical properties, photovoltaic activity

杜香莎, 李海洋, 刘恒, 李根恒, 李林科, 臧双全. 紫精修饰多功能Eu(Ⅲ)配合物的荧光开关、非线性光学和光电活性[J]. 应用化学, 2017, 34(9): 1024-1034.

DU Xiangsha, LI Haiyang, LIU Heng, LI Genheng, LI Linke, ZANG Shuangquan. Multi-Functional Viologen-Based Eu(Ⅲ) Complex with Photoswitchable Luminescence, Nonlinear Optical Properties and Photovoltaic Activity[J]. Chinese Journal of Applied Chemistry, 2017, 34(9): 1024-1034.

参考文献

[1]	Ungur L,Lin S Y,Tang J,et al.Single-Molecule Toroics in Ising-type Lanthanide Molecular Clusters[J]. Chem Soc Rev,2014,43(20):6894-6905.
[2]	Bianchi A,Delgado-Pinar E,García-España E,et al.Highlights of Metal Ion-based Photochemical Switches[J]. Coord Chem Rev,2014,260:156-215.
[3]	Irie M,Fukaminato T,Matsuda K,et al.Photochromism of Diarylethene Molecules and Crystals: Memories, Switches, and Actuators[J]. Chem Rev,2014,114(24):12174-12277.
[4]	Ratera I,Veciana J. Playing with Organic Radicals as Building Blocks for Functional Molecular Materials[J]. J Chem Soc Rev,2012,41:303-349.
[5]	Zhang T,Lin W. Metal-Organic Frameworks for Artificial Photosynthesis and Photocatalysis[J]. Chem Soc Rev,2014,43:5982-5993.
[6]	Guldi D M,Rahman G M A,Sgobba V,et al. Multifunctional Molecular Carbon Materials from Fullerenes to Carbon Nanotubes[J]. Chem Soc Rev,2006,35(5):471-487.
[7]	Train C,Gruselle M,Verdaguer M. The Fruitful Introduction of Chirality and Control of Absolute Configurations in Molecular Magnets[J]. Chem Soc Rev,2011,40(6):3297-3312.
[8]	Li P X,Wang M S,Cai L Z,et al.Rare Electron-Transfer Photochromic and Thermochromic Difunctional Compounds[J]. J Mater Chem C,2015,3(2):253-256.
[9]	Liao J Z,Zhang H L,Wang S S,et al.Multifunctional Radical-Doped Polyoxometalate-Based Host-Guest Material:Photochromism and Photocatalytic Activity[J]. Inorg Chem,2015,54(9):4345-4350.
[10]	Deng H,Doonan C J,Furukawa H,et al.Multiple Functional Groups of Varying Ratios in Metal-Organic Frameworks[J]. Science,2010,327(5697):846-850
[11]	Ryder M R,Tan J C. Nanoporous Metal Organic Framework Materials for Smart Applications[J]. J Mater Sci Technol,2014,30(13):1598-1612.
[12]	Wang M S,Xu G,Zhang Z J,et al.Inorganic-Organic Hybrid Photochromic Materials[J]. Chem Commun,2010,46(3):361-376.
[13]	Pardo R,Zayat M,Levy D. Photochromic Organic-Inorganic Hybrid Materials[J]. Chem Soc Rev,2011,40(2):672-687.
[14]	Yao Q X,Ju Z F,Jin X H,et al.Novel Polythreaded Coordination Polymer:From an Armed-Polyrotaxane Sheet to a 3D Polypseudorotaxane Array, Photo- and Thermochromic Behaviors[J]. Inorg Chem,2009,48(4):1266-1268.
[15]	Yao Q X,Pan L,Ju X H,et al.Bipyridinium Array-Type Porous Polymer Displaying Hydrogen Storage, Charge-Transfer-Type Guest Inclusion, and Tunable Magnetic Properties[J]. Chem-Eur J,2009,15(44):11890-11897.
[16]	Zhang C H,Sun L B,Zhang C Q,et al.Novel Photo- and/or Thermochromic MOFs Derived from Bipyridinium Carboxylate Ligands[J]. Inorg Chem Front,2016,3(6):814-820.
[17]	Aulakh D,Nicoletta A P,Varghese J R,et al.The Structural Diversity and Properties of Nine New Viologen Based Zwitterionic Metal-Organic Frameworks[J]. CrystEngComm,2016,18(12):2189-2202.
[18]	Deska M,Kozlowska J,Sliwa W. Rotaxanes and Pseudorotaxanes with Threads Containing Viologen Units[J]. ARKIVOC,2013:66-100.
[19]	Higuchi M,Nakamura K,Horike S,et al.Design of Flexible Lewis Acidic Sites in Porous Coordination Polymers by Using the Viologen Moiety[J]. Angew Chem,2012,124(33):8494-8497.
[20]	Lin J B,Shimizu G K H. Pyridinium Linkers and Mixed Anions in Cationic Metal-Organic Frameworks[J]. Inorg Chem Front,2014,1(4):302-305.
[21]	Aulakh D,Varghese J R,Wriedt M. A New Design Strategy to Access Zwitterionic Metal Organic Frameworks from Anionic Viologen Derivates[J]. Inorg Chem,2015,54(4):1756-1764.
[22]	Sun J K,Zhang J. Functional Metal Bipyridinium Frameworks:Self-Assembly and Applications[J]. Dalton Trans,2015,44:19041-19055.
[23]	Sun J K,Wang P,Yao Q X,et al.Solvent- and Anion-Controlled Photochromism of Viologen-Based Metal-Organic Hybrid Materials[J]. J Mater Chem,2012,22(24):12212-12219.
[24]	Sun J K,Cai L X,Chen Y J,et al.Reversible Luminescence Switch in a Photochromic Metal Organic Framework[J]. Chem Commun,2011,47(24):6870-6872.
[25]	Chen H,Zheng G,Li M,et al.Photo- and Thermo-Activated Electron Transfer System Based on a Luminescent Europium Organic Framework with Spectral Response from UV to Visible Range[J]. Chem Commun,2014,50(88):13544-13546.
[26]	Sun J K,Chen C,Cai L X,et al.Mechanical Grinding of a Single-Crystalline Metal Mrganic Framework Triggered Emission with Tunable Violet-to-Orange Luminescence[J]. Chem Commun,2014,50(100):15956-15959.
[27]	Jin X H,Sun J K,Cai L X,et al.2D Flexible Metal Organic Frameworks with [Cd2(μ2-X)2](X=Cl or Br) Units Exhibiting Selective Fluorescence Sensing for Small Molecules[J]. Chem Commun,2011,47(9):2667-2669.
[28]	Mitchell R H,Brkic Z,Sauro V A,et al.A Photochromic, Electrochromic, Thermochromic Ru Complexed Benzannulene:An Organometallic Example of the Dimethyldihydropyrene-Metacyclophanediene Valence Isomerization[J]. J Am Chem Soc,2003,125(25):7581-7585.
[29]	Li M H,Keller P. Stimuli-Responsive Polymer Vesicles[J]. Soft Matter,2009,5:927-937.
[30]	Jaffe A,Lin Y,Mao W L,et al.Pressure-Induced Conductivity and Yellow-to-Black Piezochromism in a Layered Cu-Cl Hybrid Perovskite[J]. J Am Chem Soc,2015,137(4):1673-1678.
[31]	Wu J H,Liou G S. High-Performance Electrofluorochromic Devices Based on Electrochromism and Photoluminescence-Active Novel Poly(4-Cyanotriphenylamine)[J]. Adv Funct Mater,2014,24(41):6422-6429.
[32]	Yao J,Hashimoto K,Fujishima A. Photochromism Induced in an Electrolytically Pretreated Mo03 Thin Film by Visible Light[J]. Nature,1992,355:624-626.
[33]	Irie M. Diarylethenes for Memories and Switches[J]. Chem Rev,2000,100(5):1685-1 716.
[34]	de Jong J J D,Lucas L N,Kellogg R M,et al. Astronomers Attempt to Stay in the Big League[J]. Science,2004,304(5669):378-380.
[35]	Li H Y,Xu H,Zang S Q,et al.A Viologen-functionalized Chiral Eu-MOF as a Platform for Multifunctional Switchable Material[J]. Chem Commun,2016,52(3):525-528.
[36]	Li H Y,Wei Y L,Dong X Y,et al.Novel Tb-MOF Embedded with Viologen Species for Multi-Photofunctionality:Photochromism, Photomodulated Fluorescence, and Luminescent pH Sensing[J]. Chem Mater,2015,27(4):1327-1331.
[37]	Lvaro Á,Ferrer M,Fornés V B,et al.A Periodic Mesoporous Organosilica Containing Electron Acceptor Viologen Units[J]. Chem Commun,2001,24:2546-2547.
[38]	Park Y S,Um S Y,Yoon K B. Charge-Transfer Interaction of Methyl Viologen with Zeolite Framework and Dramatic Blue Shift of Methyl Viologen-Arene Charge-Transfer Band upon Increasing the Size of Alkali Metal Cation[J]. J Am Chem Soc,1999,121(13):3193-3200.
[39]	Berthet J J,Micheau C,Metelitsa A,et al.Multistep Thermal Relaxation of Photoisomers in Polyphotochromic Molecules[J]. J Phys Chem A,2004,108(50):10934-10940.
[40]	Sheldrick G M. Acta Crystallogr,Sect. A:Fundam Crystallogr[M]. 1990,46:457.
[41]	Sheldrick G M. SHELXS-97,Program for Solution of Crystal Structures[M]. University of Göttingen,Germany,1997.
[42]	Sheldrick G M. SHELXL-97,Program for Refinement of Crystal Structures[M]. University of Göttingen,Germany,1997.
[43]	Tan Y,Fu Z Y,Zeng Y,et al.Highly Stable Photochromic Crystalline Material Based on a Close-Packed Layered Metal-Viologen Coordination Polymer[J]. J Mater Chem,2012,22(34):17452-17455.
[44]	Toma O,Mercier N,Allain M,et al.Photo- and Thermochromic and Adsorption Properties of Porous Coordination Polymers Based on Bipyridinium Carboxylate Ligands[J]. Inorg Chem,2015,54(18):8923-8930.
[45]	Matsunaga Y,Goto K,Kubono K,et al.Photoinduced Color Change and Photomechanical Effect of Naphthalene Diimides Bearing Alkylamine Moieties in the Solid State[J]. Chem Eur J,2014,20(24):7309-7316.
[46]	Xu G,Guo G C,Wang M S,et al.Photochromism of a Methyl Viologen Bismuth(Ⅲ) Chloride: Structural Variation before and after UV Irradiation[J]. Angew Chem Int Ed,2007,46(18):3249-3251.
[47]	Xu G,Guo G C,Guo J S,et al.Photochromic Inorganic-Organic Hybrid:A New Approach for Switchable Photoluminescence in the Solid State and Partial Photochromic Phenomenon[J]. Dalton Trans,2010,39(37):8688-8692.
[48]	Lin R G,Xu G Wang M S,et al. Improved Photochromic Properties on Viologen-Based Inorganic-Organic Hybrids by Using π-Conjugated Substituents as Electron Donors and Stabilizers[J]. Inorg Chem,2013,52(3):1199-1205.
[49]	Sun J K,Ji M,Chen C,et al.A Charge-Polarized Porous Metal-Organic Framework for Gas Chromatographic Separation of Alcohols from Water[J]. Chem Commun,2013,49(16):1624-1626.
[50]	Hutchison G R,Ratner M A,Marks T J. Intermolecular Charge Transfer Between Heterocyclic Oligomers. Effects of Heteroatom and Molecular Packing on Hopping Transport in Organic Semiconductors[J]. J Am Chem Soc,2005,127(48):16866-16881.
[51]	Jhang P C,Chuang N T,Wang S L. Layered Zinc Phosphates with Photoluminescence and Photochromism:Chemistry in Deep Eutectic Solvents[J]. Angew Chem Int Ed,2010,49(25):4200-4204.
[52]	Lin R G,Xu G,Lu G,et al.Photochromic Hybrid Containing In Situ-Generated Benzyl Viologen and Novel Trinuclear [Bi3Cl14]5-:Improved Photoresponsive Behavior by the <inline-graphic xlink:href="1000-0518-34-9-1024/img_9.jpg"/> Interactions and Size Effect of Inorganic Oligomer[J]. Inorg Chem,2014,53(11):5538-5545.
[53]	Yoshikawa H,Nishikiori S I,Watanabe T,et al.Polycyano-Polycadmate Host Clathrates Including a Methylviologen Dication. Syntheses, Crystal Structures and Photo-Induced Reduction of Methylviologen Dication[J]. J Chem Soc Dalton Trans,2002,43(9):1907-1917.
[54]	Jin X H,Sun J K,Xu X M,et al.Conformational and Photosensitive Adjustment of the 4,4'-Bipyridinium in Mn(Ⅱ) Coordination Complexes[J]. Chem Commun,2010,46(26):4695-4697
[55]	Sava D F,Rohwer L E S,Rodriguez M A,et al. Intrinsic Broad-Band White-Light Emission by a Tuned, Corrugated Metal-Organic Framework[J]. J Am Chem Soc,2012,134(9):3983-3986.
[56]	Xu H,Cao C S,Zhao B. A Water-Stable Lanthanide-Organic Framework as a Recyclable Luminescent Probe for Detecting Pollutant Phosphorus Anions[J]. Chem Commun,2015,51:10280-10283.
[57]	Xu H,Cao C S,Kang X M,et al.Lanthanide-Based Metal Organic Frameworks as Luminescent Probes[J]. Dalton Trans,2016,45(45):18003-18017.
[58]	Xu H,Zhai B,Cao C S,et al.A Bifunctional Europium-Organic Framework with Chemical Fixation of CO2 and Luminescent Detection of Al3+[J]. Inorg Chem,2016,55(19):9671-9676.
[59]	Li H N,Li H Y,Li L K,et al.Syntheses, Structures, and Photoluminescent Properties of Lanthanide Coordination Polymers Based on a Zwitterionic Aromatic Polycarboxylate Ligand[J]. Cryst Growth Des,2015,15(9):4331-4340.
[60]	Ma M L,Ji C,Zang S Q. Syntheses, Structures, Tunable Emission and White Light Emitting Eu3+ and Tb3+ Doped Lanthanide Metal Organic Framework Materials[J]. Dalton Trans,2013,42(29):10579-10586.
[61]	Jain K,Pratt G W. Optical Transistor[J]. Appl Phys Lett,1976,28:719-721.
[62]	Zyss J,Chemla D S. Nonlinear Optical Properties of Organic Molecules and Crystals[M]. New York:Academic Press,1989,1:23-191.
[63]	Keszler D A. Synthesis, Crystal Chemistry,Optical Properties of Metal Borates[J]. Curr Opin Solid State Mater Sci,1999,4(2):155-162.
[64]	Nye J F. Physical Properties of Crystals:Their Representation by Tensors and Matrices[M]. Clarendon,Oxford,1985.
[65]	Bella S D. Second-Order Nonlinear Optical Properties of Transition Metal Complexes[J]. Chem Soc Rev,2001,30(6):355-366.
[66]	Li P X,Wang M S,Zhang M J,et al.Electron-Transfer Photochromism to Switch Bulk Second-Order Nonlinear Optical Properties with High Contrast[J]. Angew Chem Int Ed,2014,53(43):11529-11531.